Nickel complex compounds, anions

This behaviour may suggest a sequence of reduction processes for some possible nickel complex compounds in the presence of an ionic medium containing chloride anions and ammonium cations (from the eutectic composition acting as a solvent) 0i Coop>er, 1996 Zheng et al., 2005). 

The purpose of this review is to provide the reader with a scenario of what can be accomplished with nickel complexes. It is useful to do this via a series of broad schemes, hypothetical in some cases, which show the main reaction patterns, without considering mechanistic details. Examples will illustrate the various processes, but extension to other substrates or to different conditions often requires use of alternative ligands or solvents, or a change from a neutral complex to a cationic or anionic species, as indicated above. For references to syntheses with nickel see Baker et al. (10). For criteria for the synthesis of coordination compounds and stability of organotransition metal complexes in general, see references (11. 12). Organometallic literature has been collected periodically by Bruce (13). 

Nickel compounds are of great importance industrially and a review is available on the use of nickel in heterogeneous catalysis, electroplating, batteries, pigments, ceramics and hydrogen storage.76 This concerns simple aqua complexes of nickel(II) with anions such as carbonate, halide, hydroxide, nitrate and sulfate. Nickel acetate and formate find similar use, and the acetate is employed in the sealing of anodized aluminum.77 [Ni(NH3)6]Cl2 has been shown to be potentially applicable in heat pumps.78... 

We have also observed that the sensitivity of aryl-methyl-nickel compounds la and b to oxygen is greatly enhanced by the addition of methylllthium. Under these conditions, the presence of la and b as nickelate complexes in is indicated by isotopic excliange studies. These anionic nT el complexes should be even better donors than their neutral counterparts 1,(26) and they are thus expected also to show enhanced reactivity to aryl bromides in those interactions proceeding by electron transfer. Reductive eliminations similar to those presented for 1 can be formulated as ... 

When RX is easily reduced, as in the case of allyl iodides and benzyl bromides, the competing further reduction of the intermediate radical is suppressed and radical reactions such as dimerization, addition to double bonds and aromatic compounds or reaction with anions can be favored. The radical pathway can be also promoted by catalysis with reduced forms of vitamin Bn, cobaloximes or nickel complexes. These react with the alkyl halide by oxidative addition and release the alkyl radical by homolytic cleavage. 

The name dithiolenes was chosen to describe these compounds without prejudice towards one of the limiting structures. The equally descriptive name dithienes has been coined for the same reason, but it is now rarely used. The less fortunate description of dithiolenes as dithiolato complexes is found occasionally, but it does have a much more restricted meaning (see Section 16.5.2.4) and should be avoided for the neutral species. Nevertheless, Chemical Abstracts refers to dithiolenes as bis[l,2-ethenedithiolato(2—)] complexes of the respective central metal, for example the parent nickel complex (4) is listed as nickel, bis[l,2-ethenedithiolato(2—)-5,S ]- however, depending on the date of the CA issue, its tetraphenyl derivative will be found either under bis[a,a -stilbenedithiolato(2 — )]-nickel or as bis[ 1,2-diphenyl-1,2-ethenedithiolato(2 -)-S,S"]-nick-el. Even less appropriate are the CA names for the radical anions and dianions of the dithiolenes, which are referred to as metallates(—) and metallates(2 —) of the respective ligands the dianion of the parent nickel dithiolene thus is found as bis[l,2-ethenedithiolato(2—)]-nickelate(2—), a name which has little to do with the electronic structure of the compound. 

Keim and co-workers have found that the treatment of Ni(COD)2 with both triphenylphosphine and the phosphorane, Ph3PCHC(0)Ph, affords a nickel(II) chelate complex formally derived from the enolate of Ph2PCH2C(0)Ph (Figure 7.10). ° This crystalline compound, which can be conveniently prepared on a large scale, has been characterized by single crystal X-ray diffraction. Much like o-diphenylphosphinobenzoate, the novel enolate ligand functions as an anionic P-O donor. What is particularly intriguing is that its nickel complex also efficiently catalyzes the formation of linear a-olefins from ethylene. 

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